EP3632679B1 - Polyimide laminated film roll body and method for manufacturing same - Google Patents

Polyimide laminated film roll body and method for manufacturing same Download PDF

Info

Publication number
EP3632679B1
EP3632679B1 EP18805339.1A EP18805339A EP3632679B1 EP 3632679 B1 EP3632679 B1 EP 3632679B1 EP 18805339 A EP18805339 A EP 18805339A EP 3632679 B1 EP3632679 B1 EP 3632679B1
Authority
EP
European Patent Office
Prior art keywords
polyimide film
film
polyimide
roll
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18805339.1A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3632679A4 (en
EP3632679A1 (en
Inventor
Cheolmin Yun
Hye Won Jeong
Kyungjun Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority claimed from PCT/KR2018/003070 external-priority patent/WO2018216890A1/ko
Publication of EP3632679A1 publication Critical patent/EP3632679A1/en
Publication of EP3632679A4 publication Critical patent/EP3632679A4/en
Application granted granted Critical
Publication of EP3632679B1 publication Critical patent/EP3632679B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/56—Winding and joining, e.g. winding spirally
    • B29C53/562—Winding and joining, e.g. winding spirally spirally
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
    • B32B43/003—Cutting
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a method for manufacturing a roll of a polyimide laminated film in which different kinds of polyimide films are laminated, and a roll of a laminated film.
  • Polyimide (PI) is a polymer having a relatively low crystallinity or mostly amorphous structure. It is easy to be synthesized and can be manufactured as a thin film. It is a polymer material having transparency, excellent heat resistance and chemical resistance owing to a rigid chain structure, excellent mechanical and electrical properties and dimensional stability, as well as the advantage of not requiring a crosslinking group for curing. It is widely used in electric and electronic materials such as automotive, aerospace, flexible circuit boards, liquid crystal alignment films for LCD, adhesives and coatings.
  • the polyimide resin has excellent heat resistance and mechanical characteristics, so that it is used as a substrate for various display devices such as a liquid crystal display device and an organic EL display device, for example, a large display such as a television and a small display such as a mobile phone, a personal computer and a smart phone.
  • an organic EL display device can be manufactured by replacing an existing glass substrate with a polyimide substrate to form a thin film transistor (hereinafter referred to as TFT), and then sequentially laminating an electrode, a light emitting layer, and an electrode.
  • TFT thin film transistor
  • the polyimide substrate is prepared by a solvent casting method, which involves coating of a glass substrate with a polyamic acid solution that is a polyimide precursor solution and then curing of the substrate by stepwise heating. It results in problems of a long process time and low production yield.
  • JP 2011056824 A discloses a roll of a laminated film, comprising a first polyimide film and a second polyimide film laminated on the first polyimide film and comprising a cured product of a fluorine-based, siloxane-based or amine-based polyamic acid, wherein the second polyimide film has a glass transition temperature of 350°C or more.
  • a problem to be solved by the present invention is to provide a roll of a polyimide laminated film which can more efficiently provide a polyimide substrate for a flexible display having excellent physical properties.
  • Another problem to be solved by the present invention is to provide a method for manufacturing a laminate of a polyimide film and an inorganic substrate using the roll of the laminated film.
  • the present invention also provides a method of manufacturing a flexible device using the roll of the laminated film.
  • the present invention provides a roll in which a laminated film is wound comprising
  • the thickness of the first polyimide film may be 60 to 500 ⁇ m, and the thickness of the second polyimide film may be 0.1 to 50 ⁇ m.
  • the first polyimide film has a thermal decomposition temperature of 450 °C or higher, a modulus of 9 to 11 GPa, a tensile strength of 400 to 600 MPa, a yield strength of 130 to 200 MPa, a coefficient of thermal expansion (CTE) of -20 ppm/°C to 20 ppm/°C in a temperature range of from 100 °C to 500 °C.
  • CTE coefficient of thermal expansion
  • the residual stress of the roll of the laminated film may be 0.1 MPa to 200 MPa.
  • the content of (B-1) the imino-forming compound having the structural unit represented by the above formula 7 in the component (B) may be 5 to 70% by weight based on 100% by weight of the total amount of the component (B).
  • the number average molecular weight calculated from the amine value of (B-1) the imino-forming compound having the structural unit represented by the above formula 7 in the component (B) may be 500 to 10,000.
  • the polyamic acid is obtained by reacting the component (A) and the component (B) in a molar ratio (component (B) / component (A)) of from 0.8 to 1.2.
  • the second polyimide film may have a void having a diameter of 100 nm or less and a shape of the void is a sphere having an average diameter of 10 to 50 nm, when observing the cross section of the film.
  • the second polyimide film may have an in-plane retardation of 5 nm or less.
  • the second polyimide film may have a yellowness index (YI) of 50 or less when the thickness is 50 ⁇ m.
  • YI yellowness index
  • the present invention also provides a method for manufacturing a roll of laminated film, wherein the method comprises the steps of:
  • a tensile force of 0.1 to 200 MPa may be applied to the first polyimide film.
  • the polyamic acid solution may comprise at least 50% by weight of a solvent having a positive distribution coefficient (logP) as measured at 25 °C, based on total weight of an organic solvent.
  • logP positive distribution coefficient
  • the heating and curing of the coated polyamic acid solution may be proceeded below the glass transition temperature of the second polyimide film in the range of 250 to 450 °C in a nitrogen atmosphere.
  • the present invention also provides a method of manufacturing a flexible device comprising the steps of:
  • the present invention relates to a roll manufactured by preparing a polyimide laminated film having a form in which a polyimide film formed by using a solution casting process and a high heat resistant polyimide film are stacked.
  • the roll of the laminated film manufactured as described above can continuously supply a flexible substrate having excellent physical properties, thereby improving yield and efficiency of the continuous manufacturing process of the flexible device.
  • substituted means that at least one hydrogen contained in a compound or an organic group is substituted with a substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carboxylic group, an aldehyde group, an epoxy group, a cyano group, a nitro group, an amino group, a sulfonic group or a derivative thereof.
  • a polyamic acid is coated on a glass substrate and cured by heating in an oven in a stepwise manner, which requires a long process time. Therefore, there is a problem of low production yield.
  • a polyimide film was prepared by dispersing inorganic particles such as silica particles in a polyamic acid solution for anti-blocking as shown in Fig. 1 .
  • in Fig. 1 a polyimide film was prepared by dispersing inorganic particles such as silica particles in a polyamic acid solution for anti-blocking as shown in Fig. 1 .
  • the polyimide film when a polyimide film containing such inorganic particles is laminated on a glass substrate by a hot pressing method, voids are formed on interface between the glass substrate and the film due to the inorganic particles present on the surface of the film, which reduces adhesive force between the glass substrate and the polyimide film. Therefore, the polyimide film may be raised up from the glass substrate during processes and a solution may be introduced into the interface of the polyimide film and the glass substrate during a cleaning process, so that the subsequent process may be difficult to proceed.
  • the polyimide film when a polyimide film is produced by a tenter process, a tensile force is applied only in the direction of progress.
  • the polyimide film may have a difference in physical properties between MD (longitudinal direction) and TD (width direction), causing warpage of the substrate due to heat shrinkage during the subsequent process.
  • a PET (polyethylene terephthalate) film is used as a protective film of the polyimide film for the substrate, and the heat resistance of the PET film is lower than that of the polyimide. Therefore, as shown in Fig. 2b , when used in a hot pressing process at a high temperature, shrinkage of the PET film may occur, which may cause warping of the substrate.
  • the adhesive strength to the polyimide film is increased by a hot pressing process, so that delamination may occur between the polyimide film and the inorganic substrate when the protective film is peeled off. Therefore, there are many problems when the PET protective film is used together with the polyimide film in a hot pressing process.
  • the present invention provides a roll of a laminated polyimide film and a method of manufacturing the same, which enable a flexible substrate to be continuously manufactured without using an anti-blocking agent such as inorganic particles or a PET protective film.
  • the present invention provides a roll in which a laminated film is wound comprising:
  • a roll of a laminated film in which a second polyimide film made of a fluorine-based, siloxane-based or amine-based polyamic acid and having a glass transition temperature of 350 °C or more as measured at a heating rate of 20 °C/min is laminated on a first polyimide film used as a carrier film, can provide the polyimide film as a wound roll without using an antistatic additive such inorganic particles and can be conveniently used in a continuous manufacturing process of a flexible device since it does not require a PET protective film.
  • the present invention provides a method for manufacturing the roll of the laminated film, wherein the method comprises the steps of:
  • a polyimide laminated film in which a polyimide film is formed on a polyimide substrate is prepared by a solution casting method using a polyamic acid with a self-supporting polyimide film as a substrate.
  • the thickness of the first polyimide film may be 60 to 500 ⁇ m, preferably 60 to 300 ⁇ m.
  • the polyimide film can be used alone as a supporting substrate without using a non-flexible supporting substrate such as a glass substrate in the process of manufacturing a polyimide using polyamic acid, so that it is possible to wind the polyimide substrate and the polyimide film formed on the substrate together.
  • the thickness of the first polyimide film is less than 60 ⁇ m, it may not be able to sufficiently fulfill its role as a substrate in the process of manufacturing a polyimide by the solution casting process, for example tearing or wrinkling may be occurred.
  • the thickness of the film is more than 500 ⁇ m, winding may become difficult.
  • a predetermined tensile force may be applied to the film during the introduction of the first polyimide film into the manufacturing process, for example, a tensile force of 0.1 MPa or more and 200 MPa or less or 0.1 to 100 MPa may be applied. It provides tension to the film to keep the film firm and flat so that the second polyimide film formed on the first polyimide film can be formed more evenly.
  • the first polyimide film and the second polyimide film may exhibit an adhesive strength of about 1 N/cm or more, or about 2 N/cm or more, or about 3 to 5 N/cm, and a peel strength of 0.1 N/cm or less, or about 0.001 to 0.05 N/cm by a simple cutting process.
  • the first polyimide film may be a high heat-resistant polyimide film.
  • the first polyimide film isprepared by polymerizing a tetracarboxylic dianhydride having a structure represented by the following formula 1 or 3 and a diamine having a structure represented by the following formula 2 or 4.
  • the first polyimide film may be prepared by polymerizing the tetracarboxylic dianhydride of formula 1 and the diamine of formula 2, or the tetracarboxylic dianhydride of formula 3 and the diamine of formula 4.
  • the first polyimide film has a high decomposition temperature (Td) of 450 °C or more, or 450 to 600 °C.
  • Td decomposition temperature
  • the first polyimide film has excellent heat resistance, it is possible to suppress the occurrence of warpage or other problems causing a reduced reliability of the device against high-temperature heat added during a heating process for curing and imidization of the second polyimide film and a hot pressing process as a subsequent process. And as a result, it is possible to manufacture a device having improved characteristics and reliability.
  • the first polyimide film may have a coefficient of thermal expansion (CTE) of about 20 ppm/°C or less, or about 17 ppm/°C or less, or about -20 to 20 ppm/°C in a temperature range of from 100 °C to 470 °C and a 1% thermal decomposition temperature (Td1%) of 450 °C or more, or 470 °C or more.
  • the modulus of the first polyimide film may be 9 to 11 GPa.
  • the first polyimide film may have a tensile strength of 400 to 600 MPa and a yield strength of 130 to 200 MPa.
  • the first polyimide film satisfying the above requirements is cleanly peeled off from the second polyimide film used as a flexible substrate, so that it does not affect the transparency and optical characteristics of the second polyimide film.
  • the residual stress of the laminated roll may be 0.1 MPa to 100 MPa, preferably 0.1 to 10 MPa. Such a low residual stress can suppress the warpage phenomenon of the laminated substrate.
  • the second polyimide film used in the laminated roll according to the present invention is made of a fluorine-based, siloxane-based or amine-based polyamic acid, and has a glass transition temperature of 350 °C or higher as measured at a heating rate of 20 °C/min.
  • the diamine used in the preparation of the fluorine-based, siloxane-based or amine-based polyamic acid used in the production of the second polyimide film may be a diamine containing at least one divalent organic group selected from the following formulas 5a to 5t together with the fluorine-based, siloxane-based or amine-based diamine, but is not limited to thereto.
  • At least one hydrogen atom present in the divalent organic group of formulas 5a to 5t may be substituted with a substituent selected from a halogen atom selected from -F, -CI, -Br and -I, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms.
  • a substituent selected from a halogen atom selected from -F, -CI, -Br and -I, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a hal
  • the tetracarboxylic dianhydride used in the preparation of the fluorine-based, siloxane-based or amine-based polyamic acid used in the production of the second polyimide film may be a tetracarboxylic dianhydride containing at least one tetravalent organic group selected from the following formulas 6a to 6r together with the fluorine-based, siloxane-based or amine-based tetracarboxylic dianhydride, but is not limited to thereto.
  • At least one hydrogen atom present in the tetravalent organic group of formulas 6a to 6r may be substituted with a substituent selected from a halogen atom selected from -F, -CI, -Br and -I, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms.
  • a substituent selected from a halogen atom selected from -F, -CI, -Br and -I, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms,
  • the second polyimide film produced by using the fluorine-based polyamic acid is prepared by reacting 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride and pyromellitic acid dianhydride as acid dianhydride and 2,2'-bis(trifluoromethyl)benzidine as diamine as a polymerization component.
  • the second polyimide film when the siloxane-based polyamic acid, it contains a structural unit represented by the following formula 7 in the molecular structure.
  • R 1 is independently a monovalent organic group having 1 to 20 carbon atoms and n is an integer of 1 to 200.
  • the hydrocarbon group having 1 to 20 carbon atoms for R 1 includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and specific examples thereof includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl-group, a tert-butyl group, a pentyl group, a hexyl group, etc.
  • the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group.
  • the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group and a naphthyl group.
  • Examples of the organic group having 1 to 20 carbon atoms containing an oxygen atom include an organic group containing a hydrogen atom, a carbon atom and an oxygen atom, and specific examples thereof include organic groups having 1 to 20 carbon atoms having an ether bond, a carbonyl group and an ester group.
  • Examples of the organic group having 1 to 20 carbon atoms having an ether bond include an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkoxyalkyl group having 1 to 20 carbon atoms, and the like. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group and a methoxymethyl group.
  • Examples of the organic group having 1 to 20 carbon atoms having a carbonyl group include an acyl group having 2 to 20 carbon atoms. Specific examples thereof include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.
  • Examples of the organic group having 1 to 20 carbon atoms having an ester group include an acyloxy group having 2 to 20 carbon atoms. Specific examples thereof include an acetyloxy group, a propionyloxy group, an isopropionyloxy group and a benzoyloxy group.
  • Examples of the organic group having 1 to 20 carbon atoms containing a nitrogen atom include an organic group containing a hydrogen atom, a carbon atom and a nitrogen atom, and specific examples thereof include an imidazole group, a triazole group, a benzimidazole group and a benztriazole group.
  • Examples of the organic group having 1 to 20 carbon atoms containing an oxygen atom and a nitrogen atom include organic groups containing a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom, and specific examples thereof include an oxazole group, an oxadiazole group, a benzoxazole group and a benzoxadiazole group.
  • At least one of the plurality of R 1 in formula 7 includes an aryl group in order to effectively avoid warping and twisting of the obtained polyimide-based film. More specifically, it is preferable that a plurality of R 1 are an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms.
  • the ratio of the alkyl group (i) to the aryl group (ii) in all R 1 in the structural unit (7) is within the above range, it is possible to more effectively avoid warping and twisting of the obtained polyimide-based film.
  • the alkyl group having 1 to 10 carbon atoms (i) is preferably a methyl group, and the aryl group having 6 to 12 carbon atoms (ii) is preferably a phenyl group.
  • n in formula 7 is an integer of 1 to 200, preferably 3 to 200, more preferably 10 to 200, even more preferably 20 to 150, still more preferably 30 to 100, and particularly preferably 35 to 80.
  • n in formula 7 is within the above range, the polyimide obtained from the polyamic acid is likely to form a microphase separation, so that the occurrence of warping and twisting of the obtained polyimide-based film can be suppressed, and the whitening and the reduced mechanical strength of the polyimide-based film is suppressed.
  • the polyamic acid having a structural unit (7) is obtained by reacting (A) a component comprising at least one acyl compound selected from the group consisting of a tetracarboxylic dianhydride and a reactive derivative thereof (also referred to as “component (A)") with (B) a component comprising an imino-forming compound (also referred to as “component (B)").
  • component (A) an acyl compound having a structural unit (7) (hereinafter also referred to as compound (A-1)) is used, or as the component (B), (B-1) an imino-forming compound having a structural unit (7) (hereinafter also referred to as compound (B-1)) is used. Further, both the compound (A-1) and the compound (B-1) may be used. According to this reaction, it is possible to obtain a polyamic acid according to the structure of the starting compound to be used and to obtain a polyamic acid having a structural unit derived from the compound in an amount according to the amount of the starting compound to be used.
  • the component (A) comprises at least one acyl compound selected from a tetracarboxylic dianhydride and a reactive derivative thereof.
  • it comprises at least one compound selected from the group consisting of the compound (A-1), and an acyl compound (A-2) other than the compound (A-1).
  • Specific examples of the compound (A-1) include at least one acyl compound selected from a tetracarboxylic dianhydride having a structural unit (7) and a reactive derivative thereof, preferably compounds represented by formulas 8, 8A, 8B and 8C.
  • the reactive derivative include a tetracarboxylic acid having a structural unit (7), an ester of the tetracarboxylic acid, and an acid chloride of the tetracarboxylic acid.
  • R 1 and n are each independently the same as R 1 and n in formula 7, and the preference is also the same.
  • R 2 each independently represents a divalent hydrocarbon group of 1 to 20 carbon atoms.
  • R 11 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the monovalent organic group having 1 to 20 carbon atoms includes a monovalent organic group having 1 to 20 carbon atoms for R 1 in formula 8.
  • the divalent hydrocarbon group having 1 to 20 carbon atoms for R 2 includes a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms.
  • the alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms, and examples thereof include a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and a hexamethylene group.
  • the cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.
  • the arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
  • the compound (A-1) preferably has a number average molecular weight of 200 to 10,000, more preferably 500 to 8,000.
  • the component (A) when the component (A) comprises the compound (A-1), the component (A) preferably comprises the compound (A-1) in an amount of from 10 to 60 wt% based on 100 wt% of the total acyl compound (component (A)), more preferably from 20 to 50 wt%, even more preferably from 25 to 50 wt%, particularly preferably from 30 to 50 wt%.
  • the amount of the compound (A-1) to be used is preferably within the above range.
  • the preferable amount of the compound (A-1) based on 100% by weight of the total acyl compound (component (A)) is for the case where the compound (B-1) is not used in the synthesis of the polyamic acid.
  • the compound (A-1) and the compound (B-1) are used as the raw materials in the synthesis of the polyamic acid, it is preferable that the total amount of the compound (A-1) and the compound (B-1) to be used is substantially the same as the preferable amount of the compound (A-1).
  • components containing at least one tetravalent organic group selected from the above-mentioned formulas 6a to 6r may be used together.
  • Component (B) is an imino-forming compound.
  • imino-forming compound refers to a compound which reacts with the component (A) to form an imino (group), and specific examples thereof include a diamine compound, a diisocyanate compound, a bis(trialkylsilyl)amino compound.
  • the component (B) preferably includes at least one selected from the group consisting of the compound (B-1), and the imino-forming comound (B-2) other than the compound (B-1).
  • Examples of the imino-forming compound (B-1) having a structural unit (7) include compounds represented by the following formulas 9 and 9A.
  • R 1 and n are each independently the same as R 1 and n in formula 8, and the preference is also the same.
  • R 11 is the same as R 11 in formulas 8A and 8C.
  • R 3 each independently represents a divalent hydrocarbon group of 1 to 20 carbon atoms, and examples of the divalent hydrocarbon group of 1 to 20 carbon atoms include a divalent hydrocarbon group of 1 to 20 carbon atoms for R 2 in formulas 8, 8A, 8B and 8C.
  • a number average molecular weight calculated from the amine value is preferably 500 to 10,000, more preferably 1,000 to 9,000, and even more preferably 3,000 to 8,000, from the viewpoint of obtaining polyamic acid and/or polyimide having excellent heat resistance (high glass transition temperature) and excellent water resistance.
  • the imino-forming compound (B-1) may be used singly or in combination of two or more.
  • the component (B) preferably comprises the compound (B-1) in an amount of from 5 to 70 wt% based on 100 wt% of the total imino-forming compound (component (B)), more preferably from 10 to 60 wt%, even more preferably from 15 to 55 wt%.
  • the amount of the imino-forming compound (B-1) to be used is preferably within the above range.
  • the preferable amount of the compound (B-1) based on 100% by weight of the total imino-forming compound (compound (B)) is for the case where the compound (A-1) is not used in the synthesis of the polyamic acid.
  • components containing at least one tetravalent organic group selected from the above-mentioned formulas 6a to 6r may be used together.
  • the component (A) and the component (B) are preferably reacted in the range of the molar ratio of the component (A) and component (B) (component (B)/component (A)) of 0.8 to 1.2 as a use ratio (feed ratio), more preferably in the range of 0.95 to 1.0.
  • the molar ratio of the acyl compound (A) and the imino-forming compound (B) is less than 0.8 eq (equivalent) or more than 1.2 eq, the molecular weight is reduced, making it difficult to form a polyimide-based film.
  • the siloxane-based polyamic acid for forming the second polyimide film has a silicone compound concentration of 3 to 50% calculated by the following Equation 1, more preferably 5 to 40%, and even more preferably 8 to 30%.
  • Concentration of silicone compound unit : wt% Weight of silicone compound / A Total weight of acyl compound + B Total weight of imino ⁇ forming compound ⁇ 100
  • weight of silicone compound refers to the weight of all the compounds having the structural unit represented by the above formula 1.
  • the second polyimide film made of the siloxane-based polyamic acid may have a void having a diameter of 100 nm or less and a shape of the void may be a sphere having an average diameter of 10 to 50 nm, when observing the cross section of the film.
  • a shape of void can serve as a sponge that can alleviate the warpage phenomenon of the substrate caused by the difference in CTE between the first polyimide film and the second polyimide film.
  • the in-plane retardation value of the second polyimide film is 5 nm or less, because if the thickness is 5 nm or more, the visibility to frontal reflection is affected by the reflection of light by an external light source.
  • the second polyimide film when the second polyimide film is prepared from an amine-based polyamic acid, it has an amide bond in the molecular structure and the tetracarboxylic dianhydride and/or diamine as a raw material of polyamic acid may contain an amide bond.
  • It isprepared from at least one selected from 1R,2S,4S,5R-cyclohexanetetracarboxylic dianhydride, N,N'-bis(1,2-cyclohexanedicarboxylic anhydride-4-yl)carbonyl-3,3'-diaminodiphenylsulfone (PSHT), N,N'-bis(1,2-cyclohexanedicarboxylic anhydride-4-yl)carbonyl-1,4-phenylene diamine (PPHT), N,N'-1,4-phenylenebis[1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxamide] (
  • the tetracarboxylic dianhydride and the diamine may react at a molar ratio of 1: 0.8 to 1: 1.2 or 1.1: 1 to 1: 1.1 in the preparation of the polyimic acid to be used for the production of the first polyimide film and the second polyimide film.
  • the weight average molecular weight (Mw) of the polyamic acid is preferably 10,000 to 1,000,000, more preferably 10,000 to 200,000, and still more preferably 20,000 to 150,000.
  • the number average molecular weight (Mn) is preferably 5,000 to 10,000,000, more preferably 5,000 to 500,000, and particularly preferably 20,000 to 200,000. If the weight average molecular weight or the number average molecular weight of the polyamic acid is less than the above-described lower limit, the strength of the coating film may be lowered. In addition, the coefficient of linear expansion of the obtained polyimide-based film may rise more than necessary.
  • the weight average molecular weight or the number average molecular weight of the polyamic acid exceeds the upper limit, the viscosity of the composition for forming a polyimide-based film increases, and therefore the amount of the polyamic acid which is added to the composition when the composition is coated to form a coating film is reduced, so that the precision of the film thickness such as the flatness of the resulting coating film may be deteriorated.
  • the method of reacting the tetracarboxylic dianhydride with the diamine can be carried out according to the conventional polymerization method of polyamic acid such as solution polymerization. Specifically, it can be carried out by dissolving a diamine in an organic solvent, and then adding a tetracarboxylic dianhydride to the resultant mixed solution to effect polymerization reaction.
  • the reaction can be carried out under an inert gas or a nitrogen stream and can be carried out under anhydrous conditions.
  • the polymerization reaction may be carried out at a temperature of -20 to 60 °C, preferably 0 to 45 °C. If the reaction temperature is too high, the reactivity may become high and the molecular weight may become large, and the viscosity of the polyimide precursor solution may increase, which may be disadvantageous in the process.
  • the polyimide precursor solution prepared according to the above-mentioned production method contains a solid content in such an amount that the solution has an appropriate viscosity in consideration of processability such as coatability and application properties.
  • the content of the composition can be adjusted to 5 to 20 wt%, preferably 8 to 18 wt%, more preferably 8 to 12 wt% of the total content of polyimide precursor solution.
  • the polyimide precursor solution may be adjusted to have a viscosity of 2,000 cP or more, or 3,000 cP or more, and 10,000 cP or less, preferably 9,000 cP or less, more preferably 8,000 cP or less.
  • the viscosity of the polyimide precursor solution exceeds 10,000 cP, the efficiency of defoaming at the time of forming the polyimide layer is lowered, and thus the efficiency of the process may be lowered.
  • the produced film may also have a deterioration in electrical, optical, and mechanical properties such as the lowered surface roughness due to bubble generation.
  • the organic solvent contained in the polyimide precursor solution of the present invention may be the same as the organic solvent used in the synthesis reaction.
  • the organic solvent that can be used in the polymerization reaction may be selected from the group consisting of ketones such as ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone and 4-hydroxy-4-methyl-2-pentanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; glycol ethers (Cellosolve) such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate,
  • the organic solvent may be an organic solvent having a positive distribution coefficient (logP) as measured at 25 °C.
  • the organic solvent having a positive LogP is selected from N,N-diethylacetamide (DEAc), N,N-diethylformamide (DEF), N-ethylpyrrolidone (NEP), dimethylpropionamide (DMPA), diethylpropionamide (DEPA) or a mixture thereof and it may be used alone, or may be used in combination with a solvent having a negative LogP.
  • the amount of the solvent having a positive distribution coefficient (LogP) is at least 50% by weight or at least 70% by weight based on the total weight of the solvent.
  • a distribution coefficient is predicted by summing up the degree to which a single atom constituting a molecule or a part of a molecule contributes to the LogP of a molecule. For example, it can be calculated using the ACD/LogP module of ACD/Percepta platform from ACD/Labs.
  • the ACD/Log P module uses an algorithm based on QSPR (Quantitative Structure-Property Relationship) methodology using 2D molecular structures.
  • the distribution coefficient (LogP value) of representative solvent at 25 °C is as follows. [Table 1] DEF DMF DEAc DAMc NMP NEP DMPA DEPA LogP (25°C) 0.05 -1.01 0.32 -0.75 -0.28 0.22 0.25 1.28
  • the second polyimide film may have an in-plane retardation value (Rin) of about 5 nm or less, preferably 0.05 to 5 nm, and may maintain such a value after the hot pressing process.
  • Lin in-plane retardation value
  • the second polyimide film may be formed on the first polyimide film to a thickness of 0.1 to 50 ⁇ m, preferably 5 to 30 ⁇ m.
  • the second polyimide film can be easily delaminated from the first polyimide film in the above-mentioned thickness range so that it can be utilized in the continuous manufacturing process of the substrate for a flexible device.
  • the second polyimide film may have a yellowness index (YI) of 50 or less when the thickness is 50 ⁇ m, 40 or less when the thickness is 40 ⁇ m, 30 or less when the thickness is 30 ⁇ m, 20 or less when the thickness is 20 ⁇ m, or 10 or less when the thickness is 10 ⁇ m.
  • YI yellowness index
  • a predetermined tensile force may be applied to the first polyimide film.
  • a tensile force is not applied. Therefore, the second polyimide film has a small difference in mechanical strength between the longitudinal direction (MD) and the transverse direction (TD), so that a warpage phenomenon does not occur and an in-plane retardation value of the film can be small.
  • the polyimide precursor solution is applied to a substrate and heat-treated in an IR oven, in a hot air oven or on a hot plate.
  • the heat treatment temperature may range from 300 to 450 °C, preferably from 320 to 400 °C. It may be performed in a multi-stage heating process within the above temperature range.
  • the heat treatment process may be performed for 10 to 70 min, and preferably for 10 to 60 min.
  • the polyimide constituting the first polyimide film according to the present invention may not exhibit a glass transition temperature (Tg) in the heat treatment temperature range, that is, the curing temperature range of the polyimide.
  • the first polyimide film preferably may have a thermal decomposition temperature of 400 °C or higher, more preferably 450 °C or higher.
  • the method for manufacturing the roll of the polyimide laminated film may be a roll-to-roll process.
  • the roll of the laminated film in which a polyimide substrate (first polyimide film) and a second polyimide film are combined in the manner shown in Fig. 3 can be produced.
  • the first polyimide film used as the supporting substrate can also serve as a protective film of the second polyimide film, so that there is no need for a separate step of forming a protective film, and all the problems caused by using the PET protective film can be solved.
  • the second polyimide film from the roll of the polyimide laminated film produced by the above-described method can be continuously supplied and therefore the efficiency of the process when applied to the continuous production process of the device using the polyimide film can be improved.
  • the present invention provides a method of manufacturing a flexible device comprising the steps of forming a device on the surface of the second polyimide film of the polyimide laminated film produced by the above-described production method; and delaminating the first polyimide film after forming the device.
  • Examples of the device formed on the second polyimide film include light emitting devices such as organic electroluminescence (EL) devices and thin film transistor (TFT) devices, metal wirings, and modules such as semiconductor integrated circuits.
  • EL organic electroluminescence
  • TFT thin film transistor
  • a light emitting element such as an organic EL element and a TFT element
  • a polyimide-based film it can be used as a flexible display substrate or the like.
  • a module such as a metal wiring or a semiconductor integrated circuit is formed, it can be used as a substrate for a flexible wiring.
  • a gate electrode is provided by, for example, etching a film of metal or metal oxide or the like by a sputtering method or the like.
  • the temperature forming the film of metal or metal oxide by a sputtering method or the like can be appropriately selected depending on the composition for forming the polyimide-based film to be used, the support and the device to be formed, and is preferably 210 to 450 °C, more preferably 220 to 370 °C, and more preferably 230 to 350 °C.
  • a gate insulating film such as a silicon nitride film is formed on a polyimide-based film provided with the gate electrode, for example, by a plasma CVD method. Further, an active layer including an organic semiconductor or the like is formed on the gate insulating film by a plasma CVD or the like.
  • the temperature forming a film such as a gate insulating film or an organic semiconductor by a plasma CVD method or the like can be appropriately selected depending on the composition for forming a polyimide-based film, the support, or the device to be formed, and is preferably 210 °C to 400 °C, more preferably 220 to 370 °C, and more preferably 230 to 350 °C.
  • a film of metal or a metal oxide is formed on the active layer by a sputtering method or the like and then etched to provide a source electrode and a drain electrode.
  • a silicon nitride film or the like is formed by a plasma CVD method or the like to form a protective film. Accordingly, a thin film transistor device can be manufactured.
  • the TFT device is not limited to this type, but may be a top gate type or the like.
  • the gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are formed of a conductive material.
  • the conductive material include metals and metal oxides.
  • Examples of the metal include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony, tantalum, indium, aluminum, zinc, magnesium and alloys thereof.
  • Examples of metal oxide include ITO, IZO, ZnO and In 2 O 3 .
  • a conductive polymer may be used as the conductive material.
  • a metal oxide is preferable because a transparent electrode can be formed.
  • an insulating layer, a first electrode, an organic semiconductor layer, a second electrode and a protective layer are sequentially formed from the side of the film surface on the polyimide-based film.
  • a metal wiring can be provided by providing a copper layer on a polyimide-based film by, for example, a lamination method or a metallizing method, and treating the copper layer by a known method.
  • a copper layer can be provided by hot pressing a metal foil such as a copper foil on the film.
  • a seed layer containing a Ni-based metal and binding to the polyimide-based film is formed by, for example, a vapor deposition method or a sputtering method.
  • a copper layer having a predetermined thickness can be formed by a wet plating method or the like.
  • the second polyimide film produced by the method according to the present invention is excellent in heat resistance and excellent in adhesion with a support, so that it is possible to obtain a substrate having a wide range of applicable temperatures for forming a device on the film and having excellent performance.
  • the second polyimide film on which the device is formed may be laminated on the inorganic substrate, and then the first polyimide film may be delaminated.
  • the second polyimide film is cut from the polyimide laminated film to a predetermined size and then detached from the first polyimide film which is used as a base material, and forming a laminate with an inorganic substrate by hot pressing on the inorganic substrate.
  • the surface of the second polyimide film of the polyimide laminated film is contacted on an inorganic substrate and then hot pressed to laminate the polyimide laminated film on the inorganic substrate; the polyimide laminated film is cut to a predetermined size to reduce the adhesive strength between the first polyimide film and the second polyimide film; and the first polyimide film is separated from the second polyimide film.
  • a roll of a laminated film is directly introduced into a continuous process, followed by a hot pressing process, and then cut to a predetermined size to separate the first polyimide film from the second polyimide film adhered on the inorganic substrate.
  • the PET film used as a conventional protective film has low heat resistance. Therefore, when it is used as it is in a hot pressing process, warpage of the substrate can be caused by deformation such as shrinkage. In addition, the adhesion force of the protective film to the polyimide film is increased, so that the protective film is difficult to be delaminated, and the delamination may occur at the interface between the inorganic substrate and the polyimide film. In the present invention, since the polyimide film having high heat resistance is used as a protective film, there is little or no change in physical properties even in a hot pressing process at a high temperature.
  • the degree of warpage of the laminate after the hot pressing process may be 30 ° or less with respect to the end of the substrate, for example, the degree of warpage may be 0.1 to 15 °.
  • the degree of warpage refers to the degree of the angle of the substrate rising from both ends with respect to a horizontal line connecting the both ends of the substrate. It is possible to provide a more uniform and flat laminate owing to little warpage.
  • the step of cutting the polyimide laminated film may be performed by laser cutting or diamond scribing, but any method capable of cutting the film can be used without limitation.
  • peel strength and adhesion force according to the present invention can be measured under the conditions shown in Table 2 below.
  • 'adhesion force' means the adhesive force of the first polyimide film to the second polyimide film before the cutting process
  • 'peel strength' means the adhesion force of the first polyimide film to the second polyimide film after the cutting process.
  • the peel strength of the laminated film is obtained by preparing a sample of the laminate of the first and second polyimide films or a laminate of the polyimide laminated film laminated on a glass substrate, cutting the polyimide laminated film into a rectangular shape having a width of 10 mm, then measuring the force applied when the end portion of the cut first polyimide film is pulled off from the second polyimide film at an angle of 90 ° with the above-described measuring instrument and conditions.
  • the adhesive force before cutting was obtained by preparing a sample of the polyimide laminated film or a polyimide laminated film laminated on a glass substrate, attaching a tape having a width of 10 mm to the end portion of the first polyimide film of the sample, and pulling the end of the tape to measure the force applied when the first polyimide film is peeled off from the second polyimide film at an angle of 90 °.
  • the force measuring instrument and conditions may be the same as those of the measuring instrument and conditions for measuring the peel strength shown in Table 2.
  • the polyimide laminated film according to the present invention does not require a laser or light irradiation step or a dissolution step, does not require the use of a release agent for facilitating peeling and allows the first polyimide film to be easily peeled off from the second polyimide film only by a simple cutting process.
  • the hot pressing process may be performed at a nip pressure of 10 to 300 kN/m at a processing temperature of 400 °C to 500 °C, but is not limited thereto.
  • the nip pressure refers to the pressure that is applied to the side of the roll in contact with the substrate in the lamination process and it means the pressure per unit length of the roll, assuming that the surface on which the roll and the substrate come into contact is taken as a line.
  • the peel strength of the first polyimide film and the second polyimide film is preferably equal to the peel strength before the hot pressing process, and may be, for example, about 0.3 N/cm or less, for example, about 0.2 N/cm or less, or about 0.1 N/cm or less, or about 0.001 to 0.05 N/cm.
  • the inorganic substrate may be a glass substrate, a metal substrate such as a stainless steel substrate, or a multilayered structure of two or more layers.
  • a glass substrate which can be most easily applied to a manufacturing process of a glass substrate is preferable.
  • a composition comprising 20 wt% of a polyamic acid resin prepared by polymerizing 1 mol of BPDA and 0.99 mol of PDA, and 80 wt% of DMAc as a solvent was cast on a support. Then, the drying step at a temperature of 120 °C and the curing step (for 30 minutes) at a temperature of 150 °C - 230 °C - 300 °C - 480 °C were successively carried out to prepare a roll of a first polyimide film having a width of 600 mm for use as a carrier substrate having a thickness of 60 microns.
  • composition for forming a second polyimide film was prepared containing 10% by weight of a polyamic acid resin prepared by polymerizing 0.12 mol of 6FDA, 0.55 mol of PMDA and 0.66 mol of TFMB, and 90% by weight of DEAc as a solvent.
  • the composition for forming the second polyimide film was applied (cast) to have a thickness of 10 ⁇ m after dyring.
  • the drying step at 100 °C and the curing step at 400 °C for 30 min were successively carried out to form a second polyimide film on the first polyimide film.
  • the laminate of the first and second polyimide films was wound at a winding speed of 0.1 m/min to obtain a roll of the polyimide laminated film.
  • the second polyimide film side of the polyimide laminated film prepared in Example 1 was brought into contact with a glass substrate having a size of (370 ⁇ 470 mm), and then heated and pressed at a temperature of 350 °C at a pressure of 75 KN/m to laminate the polyimide laminated film on an inorganic substrate.
  • the polyimide laminated film of the laminate was cut to such an extent that the first polyimide film was not cut off.
  • the second polyimide film was delaminated from the first polyimide film to obtain a laminate in which the second polyimide film is laminated on the glass substrate.
  • a roll of the polyimide laminated film and a laminate with an inorganic substrate were prepared in the same manner as in Examples 1 and 2 except that PMDA-ODA was used as the first polyimide film.
  • the physical properties of the film and the laminate are measured as follows.
  • the mechanical properties (modulus, maximum stress, and maximum elongation) of the film were measured using UTM from Instron. Specifically, the film was cut to 5 mm ⁇ 60 mm or more, and then the gap between the grips was set at 40 mm. While pulling the sample at a rate of 20 mm/min, tensile strength and other mechanical properties were examined (KS M ISO 527).
  • the thickness retardation (R th ) and the in-plane retardation (Ro) were measured by Axoscan.
  • CTE coefficient of thermal expansion
  • dimensional change of the film were measured using Q400 from TA instruments.
  • a 15-micron thick film was prepared in a size of 5 mm ⁇ 20 mm, and the sample was loaded using an accessory.
  • a length of the actually measured film was equal to 16 mm.
  • a pulling force was set at 0.02 N.
  • a measurement starting temperature was 30 °C and the temperature was raised to 300 °C at a rate of 5 °C/min, then lowered to 80 °C at a rate of -5 °C/min, and again raised to 450 °C at a rate of 5 °C/min.
  • a coefficient of linear thermal expansion in the MD and TD directions of the polyimide-based film was determined as an average value in the range of 100 to 400 °C.
  • Tg the inflection point of the curve was defined as measured at a heating rate of 20°C/min.
  • HLC-8020 type GPC apparatus manufactured by TOSOH was used for measurement.
  • NMP N-methyl-2-pyrrolidone
  • the molecular weight in terms of polystyrene was determined at a measurement temperature of 40 ° C.
  • the polyimide-based film delaminated from the support was cut out to a size of 40 ⁇ 40 mm.
  • a case where the warpage (The obtained polyimide-based film was placed on a horizontal substrate and the separation distance between the film and the substrate at the four corners of the film was measured. An average value of measurements was taken as the warpage.) is less than 1.0 mm is indicated by [ ⁇ ], a case where the warpage is 1.0 mm or more and less than 2.0 mm is indicated by [O], a case where the warpage is 2.0 mm or more and less than 3.0 mm is indicated by [ ⁇ ], and a case where the warpage is 3.0 mm or more is indicated by [X].
  • a roll of the polyimide laminated film and a laminate with an inorganic substrate were prepared in the same manner as in Examples 1 and 2 except that 0.27 mol of 6FDA and 0.26 mol of TFMB were used for forming a first polyimide film.
  • a roll of the polyimide laminated film and a laminate with an inorganic substrate were prepared in the same manner as in Example 1 except that a composition for forming a second polyimide film comprising 10 wt% of a polyamic acid resin prepared by polymerizing 0.0019 mol of a dual-end type amino-modified methylphenyl silicone (DMS-DPS, Shin-Etsu Chemical Co., Ltd., number average molecular weight: 5500), 0.0988 mol of TFMB, 0.05 mol of BPAF and 0.058 mol of PMDA and 90 wt% of DEAc as a solvent was used.
  • DMS-DPS dual-end type amino-modified methylphenyl silicone
  • Fig. 5 is a SEM image of the cross section of the second polyimide film.
  • the void has a diameter of 100 nm or less and a spherical shape with an average diameter of 10 to 50 nm.
  • a roll of the polyimide laminated film and a laminate with an inorganic substrate were prepared in the same manner as in Example 1 except that a composition for forming a second polyimide film comprising 10 wt% of polyamic acid resin prepared by polymerizing 0.067 mol of PMDA-HS and 0.067 mol of DABA and 90 wt% of DEAc as a solvent was used.
  • a roll of the polyimide laminated film and a laminate with an inorganic substrate were prepared in the same manner as in Example 1 except that a composition for forming a second polyimide film comprising 10 wt% of polyamic acid resin prepared by polymerizing 0.136 mol of BPDA and 0.134 mol of PDA and 90 wt% of DEAc as a solvent was used.
  • the first polyimide film used in the production of the roll according to the Examples has excellent physical properties such as 1% thermal decomposition temperature, modulus, tensile strength, yield strength and coefficient of thermal expansion.
  • Table 4 shows the results of measurement of glass transition temperature, in-plane retardation, residual stress of the laminate of the first polyimide film and the second polyimide film prepared in Examples and Comparative Examples.
  • the laminated films according to Comparative Examples 1 and 2 were not suitable for the continuous process due to generation of the curling phenomenon due to high residual stress after winding or the impossibility of film peeling.
  • the films according to Examples have a yellowness of 10 or less when the thickness is 10 ⁇ m, show almost no difference in CTE in the MD and TD directions, and have low residual stress and small warpage, and therefore they are suitable for continuous processing.
  • a polyimide laminated film in which a polyimide film formed by using a solution casting process and a high heat-resistant polyimide film are stacked.
  • the laminated film is wound to produce a roll without delamination process. It is possible to continuously produce a laminate in which the polyimide film is laminated on a glass substrate by using a hot pressing method, thereby improving yield and efficiency of the process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP18805339.1A 2017-05-24 2018-03-16 Polyimide laminated film roll body and method for manufacturing same Active EP3632679B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR20170064367 2017-05-24
KR1020180020865A KR102018455B1 (ko) 2017-05-24 2018-02-22 폴리이미드 적층필름 롤체 및 그 제조 방법
PCT/KR2018/003070 WO2018216890A1 (ko) 2017-05-24 2018-03-16 폴리이미드 적층필름 롤체 및 그 제조 방법

Publications (3)

Publication Number Publication Date
EP3632679A1 EP3632679A1 (en) 2020-04-08
EP3632679A4 EP3632679A4 (en) 2020-09-30
EP3632679B1 true EP3632679B1 (en) 2022-03-09

Family

ID=64669303

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18805339.1A Active EP3632679B1 (en) 2017-05-24 2018-03-16 Polyimide laminated film roll body and method for manufacturing same

Country Status (6)

Country Link
US (1) US11248098B2 (ja)
EP (1) EP3632679B1 (ja)
JP (1) JP6870801B2 (ja)
KR (1) KR102018455B1 (ja)
CN (1) CN110121420B (ja)
TW (1) TWI668103B (ja)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102202472B1 (ko) * 2019-06-11 2021-01-13 피아이첨단소재 주식회사 폴리이미드 필름 및 폴리이미드 필름의 제조방법
JP2023527141A (ja) * 2020-11-19 2023-06-27 エルジー・ケム・リミテッド ディスプレイ装置用またはフレキシブルディスプレイ装置用基板、およびディスプレイ装置またはフレキシブルディスプレイ装置
KR102643076B1 (ko) * 2020-11-19 2024-03-04 주식회사 엘지화학 디스플레이 장치용 또는 플렉서블 디스플레이 장치용 기판, 및 디스플레이 장치 또는 플렉서블 디스플레이 장치
CN114030261A (zh) * 2021-11-17 2022-02-11 江苏泰祥电线电缆有限公司 一种电线电缆用绝缘复合膜的制备方法
TWI800261B (zh) * 2022-02-15 2023-04-21 台虹科技股份有限公司 卷狀層疊體的製造方法

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010094983A (ja) 2008-09-16 2010-04-30 Toyobo Co Ltd 積層ポリイミドフィルム
JP5254752B2 (ja) 2008-11-11 2013-08-07 株式会社カネカ 多層ポリイミドフィルム
JP2010150379A (ja) * 2008-12-25 2010-07-08 Jsr Corp ポリイミド系材料、フィルム及び組成物、並びにその製造方法
JP5410895B2 (ja) 2009-09-11 2014-02-05 新日鉄住金化学株式会社 ポリイミドフィルムの製造方法
JP5410894B2 (ja) * 2009-09-11 2014-02-05 新日鉄住金化学株式会社 ポリイミドフィルムの製造方法
KR20130080432A (ko) * 2010-03-31 2013-07-12 제이에스알 가부시끼가이샤 폴리이미드 전구체, 상기 전구체를 포함하는 수지 조성물 및 수지 조성물을 이용한 막 형성 방법
KR101299651B1 (ko) * 2010-07-14 2013-08-23 주식회사 엘지화학 저온 경화가 가능한 폴리이미드 수지 및 이의 제조 방법
CN102336910B (zh) 2010-07-14 2015-04-08 株式会社Lg化学 可低温固化的聚酰亚胺树脂及其制备方法
KR101478301B1 (ko) * 2011-08-30 2014-12-31 주식회사 엘지화학 고분자 수지 조성물, 폴리이미드 수지 필름, 폴리이미드 수지 필름의 제조 방법, 금속 적층체 및 회로 기판
JP5782924B2 (ja) 2011-08-30 2015-09-24 東洋紡株式会社 ポリアミドイミドフィルムの製造方法
US20150017370A1 (en) * 2011-09-12 2015-01-15 Toray Industries, Inc. Polyimide resin, resin composition and laminated film that use same
KR20150023728A (ko) * 2012-06-19 2015-03-05 신닛테츠 수미킨 가가쿠 가부시키가이샤 표시장치 및 그 제조방법, 그리고 표시장치 지지기재용 폴리이미드 필름 및 그 제조방법
JP5946348B2 (ja) 2012-07-20 2016-07-06 新日鉄住金化学株式会社 透明導電性フィルム及びその製造用ポリイミドフィルム
CN104582960B (zh) 2012-09-14 2017-03-08 三井化学株式会社 透明聚酰亚胺叠层体及其制造方法
JP5931672B2 (ja) 2012-09-24 2016-06-08 新日鉄住金化学株式会社 ポリイミド積層体及びその製造方法
JP6067419B2 (ja) 2013-02-28 2017-01-25 新日鉄住金化学株式会社 積層部材の製造方法
US9902810B2 (en) * 2013-04-03 2018-02-27 Mitsui Chemicals, Inc. Polyamic acid, varnish comprising same and polyimide film
KR20140122207A (ko) * 2013-04-09 2014-10-17 주식회사 엘지화학 적층체 및 이를 이용하여 제조된 기판을 포함하는 소자
KR101797806B1 (ko) * 2015-02-09 2017-11-14 주식회사 엘지화학 폴리이미드계 용액 및 이를 이용하여 제조된 폴리이미드계 필름
CN107522860B (zh) 2014-05-30 2020-09-25 株式会社Lg化学 聚酰亚胺基液体和使用其制备的聚酰亚胺基膜
JP6254274B2 (ja) * 2014-06-25 2017-12-27 旭化成株式会社 空隙を有するポリイミドフィルム及びその製造方法
KR102207876B1 (ko) 2014-11-25 2021-01-26 동우 화인켐 주식회사 권취 가능한 광학 다층필름
CN106133025B (zh) * 2015-03-05 2019-03-12 株式会社Lg化学 用于生产光电器件的柔性板的聚酰亚胺膜的组合物
TWI572479B (zh) * 2015-07-07 2017-03-01 律勝科技股份有限公司 包含聚醯亞胺樹脂之金屬積層板及其製造方法
JP6808401B2 (ja) 2015-08-31 2021-01-06 日鉄ケミカル＆マテリアル株式会社 機能層付きポリイミド基板フィルムの製造方法
JP6937557B2 (ja) 2015-09-30 2021-09-22 日鉄ケミカル＆マテリアル株式会社 ポリイミドフィルムの製造方法
KR102421570B1 (ko) 2015-10-02 2022-07-15 에스케이이노베이션 주식회사 폴리머 필름의 제조방법

Also Published As

Publication number Publication date
JP2020506081A (ja) 2020-02-27
KR20180128828A (ko) 2018-12-04
CN110121420A (zh) 2019-08-13
EP3632679A4 (en) 2020-09-30
TWI668103B (zh) 2019-08-11
KR102018455B1 (ko) 2019-09-04
JP6870801B2 (ja) 2021-05-12
EP3632679A1 (en) 2020-04-08
TW201900392A (zh) 2019-01-01
US20200040152A1 (en) 2020-02-06
US11248098B2 (en) 2022-02-15
CN110121420B (zh) 2022-11-01

Similar Documents

Publication Publication Date Title
EP3632679B1 (en) Polyimide laminated film roll body and method for manufacturing same
KR102392962B1 (ko) 적층부재의 제조 방법
US10647883B2 (en) Polyimide-based solution and polyimide-based film produced using same
CN108699242B (zh) 聚酰亚胺前体溶液及其制造方法
US7871554B2 (en) Process for producing polyimide film
EP2985144B1 (en) Laminate, and element comprising substrate manufactured using same
KR101775204B1 (ko) 폴리이미드계 용액 및 이를 이용하여 제조된 폴리이미드계 필름
KR102067856B1 (ko) 폴리이미드 전구체 조성물 및 이로부터 제조된 투명 폴리이미드 필름
KR101748931B1 (ko) 폴리이미드계 필름 형성용 조성물 및 이를 이용하여 제조된 폴리이미드계 필름
EP3666780B1 (en) Siloxane compound and polyimide precursor composition comprising same
CN113201219B (zh) 聚酰亚胺前体组合物和聚酰亚胺膜/基材层积体
KR101797806B1 (ko) 폴리이미드계 용액 및 이를 이용하여 제조된 폴리이미드계 필름
KR102188949B1 (ko) 폴리이미드 전구체 및 이를 이용하는 폴리이미드 필름
KR20190038382A (ko) 폴리이미드 필름 및 금속장 적층체
JP7461145B2 (ja) 樹脂組成物、ポリイミド、及びポリイミドフィルムの製造方法
KR101754449B1 (ko) 폴리이미드계 필름 및 이의 제조방법
JP7235157B1 (ja) ポリイミド前駆体組成物、ポリイミドフィルムおよびポリイミドフィルム／基材積層体
JP2007301781A (ja) 金属化ポリイミドフィルムおよび回路基板
WO2023190555A1 (ja) ポリイミド前駆体組成物、ポリイミドフィルムおよびポリイミドフィルム／基材積層体
KR20220158783A (ko) 폴리이미드 전구체 조성물 및 폴리이미드 필름/기재 적층체
KR20230106702A (ko) 폴리이미드 전구체 조성물, 폴리이미드 필름 및 폴리이미드 필름/기재 적층체
CN118139913A (zh) 聚酰亚胺前体组合物、聚酰亚胺膜和聚酰亚胺膜/基材层积体
JP2007320059A (ja) 金属化ポリイミドフィルムおよび回路基板

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190701

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIC1 Information provided on ipc code assigned before grant

Ipc: B29C 53/56 20060101ALI20200520BHEP

Ipc: B32B 37/06 20060101ALI20200520BHEP

Ipc: B32B 38/10 20060101ALI20200520BHEP

Ipc: B32B 38/00 20060101ALI20200520BHEP

Ipc: B32B 27/28 20060101ALI20200520BHEP

Ipc: B32B 43/00 20060101ALI20200520BHEP

Ipc: B32B 37/24 20060101AFI20200520BHEP

Ipc: B32B 27/08 20060101ALI20200520BHEP

Ipc: B32B 37/10 20060101ALI20200520BHEP

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20200831

RIC1 Information provided on ipc code assigned before grant

Ipc: B32B 27/08 20060101ALI20200825BHEP

Ipc: B32B 38/00 20060101ALI20200825BHEP

Ipc: B32B 37/06 20060101ALI20200825BHEP

Ipc: B32B 37/24 20060101AFI20200825BHEP

Ipc: B32B 37/10 20060101ALI20200825BHEP

Ipc: B29C 53/56 20060101ALI20200825BHEP

Ipc: B32B 27/28 20060101ALI20200825BHEP

Ipc: B32B 38/10 20060101ALI20200825BHEP

Ipc: B32B 43/00 20060101ALI20200825BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20210430

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20211122

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1473790

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018032073

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20220309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220609

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220609

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1473790

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220610

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220711

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220709

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220331

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018032073

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220316

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220316

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220331

26N No opposition filed

Effective date: 20221212

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230221

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220309

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240220

Year of fee payment: 7

Ref country code: GB

Payment date: 20240220

Year of fee payment: 7